pubs.acs.

org/journal/ascecg Research Article

Synthesis, Characterization, and Physicochemical Performance of

Nonionic Surfactants via PEG Modification of Epoxides of Alkyl
Oleate Esters
Joseph K. Ogunjobi,* Thomas J. Farmer, James H. Clark, and Con Robert McElroy*
Cite This: ACS Sustainable Chem. Eng. 2023, 11, 1857−1866 Read Online

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ABSTRACT: The synthesis of surfactants from fatty acid esters via epoxide chemistry has been known for its accompanying
challenges, which usually involve the use of toxic homogeneous catalysts in the ring-opening reaction step and generation of many
side reaction products. This paper presents environmentally benign routes to a library of nonionic surfactants via a three-step
synthesis involving transesterification of methyl oleate to alkyl oleates, epoxidation of the oleate alkene, and solventless
heterogeneously catalyzed ring opening of the epoxides with poly(ethylene glycols) of varying chain length under a short reaction
time (60 min). The processes were highly atom efficient and afforded a minimum surfactant yield of 80% with limited or negligible
side reaction products. The intermediate molecules and synthesized surfactants were purified and comprehensively characterized,
including physicochemical measurements: dynamic surface tension and equilibrium surface tension. Additionally, the hydrophilic−
lipophilic balance (HLB) concept was used to comprehensively scan through the polarity behaviors of the surfactants’ head and tail
in solution as a prediction of their end use. The results showed that surfactants have a critical micelle concentration (CMC) lower
than 0.1 mg/ml as the alkyl oleate increases in length from ethyl to decyl and that the lower-molecular-weight surfactants reached
equilibrium faster than the higher-molecular-weight surfactants. HLB results showed that the surfactants can be applied as oil-in-
water emulsifiers, detergents, solubilizers, and wetting agents. In general, the synthesized surfactants potentially possess switchable
properties for use in industrial formulations, as the alkyl chain length and the ethylene oxide number in the surfactant’s structure are
varied.
KEYWORDS: biobased chemical, heterogeneous catalyst, spectroscopy, surface tension, ring opening, oleic acid, transesterification

■ INTRODUCTION
Oleic acid is arguably the most abundant mono-unsaturated
fatty acid found in nature. It is largely found as triglycerides in
vegetable oils such as rapeseed oil, sunflower oil, olive oil, and
peanut oil and is also present in many animal fats. Oleic acid is
a C18 molecule whose ester derivatives have found wide
applications in home and personal care product industries as
the hydrophobic component in surfactants. Oleate-derived
surfactants are considered more biodegradable than any other
surfactants whose hydrophobes are from petroleum feedstock;
the oleate being incorporated makes the hydrophobic region of
the surfactants long and bulky enough to lower the CMC and
decrease the surfactant dosage used by consumers.1−5
Epoxidation is one of the means of functionalizing
unsaturated fatty esters, with many different approaches
© 2023 The Authors. Published by
American Chemical Society
1857
presented in the literature. The typical oxidants used include
chlorohydrin, organic peroxides, and peracids, but there has
been a growing need to curtail the side reaction products and
use of toxic and hazardous reagents and oxidants.6−9
Challenges in fatty ester epoxidation include hydrolysis of
the ester group, with low yields resulting from acid-catalyzed
ring-opening side reactions, separation of acidic byproducts,
Received: October 20, 2022
Revised: January 13, 2023
Published: January 26, 2023
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ACS Sustainable Chemistry & Engineering
and corrosion of reaction vessels.10 Hydrogen peroxide is a
relatively environmentally benign oxidant that has a high
content of active oxygen, decomposes to give water as the only
byproduct, and is not expensive.11,12 This increased content of
active oxygen means the use of hydrogen peroxide is a more
atom economic (AE) epoxidation process. For example, the
AE in soybean oil epoxidation using hydrogen peroxide is 90%,
which is a significant improvement as against using meta-
chloro peroxy benzoic acid, where AE = 51%.13
One of the earliest studies of functionalizing epoxidized fatty
esters via ring opening of the epoxy ring resulting in
amphiphilic compounds was reported by Hedman and co-
workers.14 In their report, methyl oleate epoxide was ring-
opened with different monomethylated polyethylene ethers
using a homogeneous boron trifluoride catalyst. Other studies
have reported epoxy ring opening of methyl and ethyl oleate
epoxides with nucleophiles such as alkyl glycosides and
oligoethene glycols using erbium(III) triflate and tin
tetrachloride as catalysts.15,16 However, these syntheses
employed catalysts and solvents that present issues such as
difficulty in removal and reuse of the catalyst, corrosiveness,
and toxicity. Recently, functionalization of the double bond of
the fatty ester unit of lactonic sophorolipid via epoxy ring
opening with polyethylene glycols was demonstrated.17 The
resulting surfactants gave promising results that could further
be exploited in personal and home care products. A
comprehensive list of the nucleophiles most commonly used
to functionalize fatty derivatives, as well as the chemistry of
fatty epoxide ring-opening reactions leading to valuable
chemicals was recently reported by Moser and co-workers.18
The properties of surfactants resulting from epoxy ring
opening of methyl oleate epoxide such as earlier reported can
be tailored to have a more hydrophilic influence and to give a
broader application by introducing polyethylene glycol (PEG)
of varying chain lengths. PEGs are short-chain polyethers
soluble in water and a number of organic solvents, including
toluene, acetone, ethanol, and dichloromethane, depending on
their molecular weight. They are nontoxic and are readily
available in various functionalities such as amine, hydroxyl, and
thiol end groups.19 Additionally, increasing the alkyl chain
length of the ester of oleic acid and ring opening its epoxide
will lead to systems with a nonpolar moiety having two
unequal chain lengths, about the same size for the methyl ester,
but with more different sizes as the alkyl length changes.
Consequently, it would be interesting to investigate how this
chemical modification will influence the physicochemical
performances and as such end use of the targeted oligomeric
surfactants when compared with the methyl oleate-based
molecule.
Hence, herein methyl oleate was transesterified into various
oleate ester analogues. The oleate alkenes were epoxidized and
the resulting epoxides subsequently ring-opened with PEGs of
varying chain length to generate a range of nonionic
surfactants. The synthetic routes employed involve the use of
recoverable heterogeneous catalysts and an atom economic
oxidant, H2O2.
■ EXPERIMENTAL SECTION
Reagents. Titanium(IV) isopropoxide; silica-supported boron
trifluoride; iron(III) nitrate nonahydrate; iron(III) chloride; PEG
400; PEG av. Mn 950-1050; PEG 1500; aluminum nitrate
hexahydrate; ammonium-Y-zeolite; phosphotungstic acid hydrate
(PTA); tungsten powder; >30% hydrogen peroxide solution in
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H2O; Adogen 464; Celite 545 coarse molecular sieve; cyclohexene
oxide Amberlyst 15 ion exchange resin; and 2-methoxyethanol were
all purchased from Sigma-Aldrich. Triethylene glycol was purchased
from Acros Organics. Polyethylene glycol monomethyl ether
(MePEG) 400 and MePEG 750 were purchased from Alfa-Aesar,
with the numbers 400 and 750 referring to the average molecular
weights of the MePEG. Orthophosphoric acid and ethanediol were
purchased from Fisher Scientific.
Preparation of Catalysts. Potassium fluoride on alumina (KF/
Al2O3), treated magnesium oxide catalyst (MgO-T600), Fe-
montmorillonite catalyst (Fe-mont), Fe-K30-montmorillonite catalyst
(Fe-K30mont), and Al-Y zeolite catalyst were prepared as described
in the Supporting Information (SI) section 3.0.
Synthesis of Alkyl Oleates from Methyl Oleate. Methyl oleate
(MO, 20 g, 67.2 mmol) and the desired alcohol (403 mmol) were
weighed into a 250 mL round-bottom flask fitted with a Dean-Stark
trap and condenser. Ti(O-i-Pr)4 or KF/Al2O3 or MgO-T600 (2 g, 10
wt % with respect to MO) was added and the reaction was agitated
under reflux. The reaction progression was monitored by GC-FID. 2
mL of the corresponding alcohol was added at 1-h intervals for the
first 3 h into the reaction. After 24 h, the resulting product was
vacuum filtered to recover the KF/Al2O3 catalyst and a rotary
evaporator was used to remove the solvent to yield an amber oil. For
reactions involving Ti(O-i-Pr)4, 25 mL of distilled water was added to
the reaction product to generate titanium(IV) oxide and isopropanol,
and the resulting solution was transferred into a separating funnel and
shaken with dichloromethane. The organic phase was collected, dried
over anhydrous magnesium sulfate, filtered, and the solvent removed
in vacuo to yield an amber oil. For the MgO-T600 catalyst, after 24 h,
the resulting product was allowed to cool down and centrifuged at
3500 rpm at 20 °C for 20 min. The supernatant was transferred into a
round-bottom flask and a rotary evaporator was used to remove the
solvent to yield an amber oil. Purity and product identification were
confirmed by GC-FID, GC-MS, IR spectroscopy, ESI-MS, and 1H
and proton-decoupled 13C NMR spectroscopy as provided in the SI.
Synthesis of Alkyl Oleate Epoxides. The desired alkyl oleate
(100.15 mmol), hydrogen peroxide solution (>30% H2O2, 40 mL),
water (30 mL), phosphotungstic acid (6 wt % with respect to alkyl
oleate), and Adogen 464 (3 wt % with respect to alkyl oleate) were
added into a 250 mL round-bottom flask and heated at 50°C with
vigorous stirring for 3 h. The resulting product was extracted in ethyl
acetate (EtOAc, 50 mL), transferred into a separating funnel, and
then washed with deionized water (30 mL). The organic layer was
dried over anhydrous magnesium sulfate, filtered, and the filtrate
passed through a plug of neutral alumina. EtOAc was removed in
vacuo to yield a light amber oil. The product was analyzed by IR
spectroscopy, GC-MS, ESI-MS, 1H and proton-decoupled 13C NMR
spectroscopy, and quantified by GC-FID as provided in the SI.
Ring Opening of Alkyl Oleate Epoxides with Polyethylene
Glycol (diol) or Polyethylene Glycol Monomethyl Ether.
Polyethylene glycol (PEG, 10 mmol) or polyethylene glycol
monomethyl ether (MePEG, 10 mmol) was heated to 80 °C in a
50 mL round-bottom flask followed by addition of catalyst (5 wt % of
PEG or MePEG) and allowed to mix thoroughly for 2 min. The
desired alkyl oleate epoxide (5 mmol) was added in drops through a
dropping funnel for over 5−10 min and the temperature was raised to
100 °C while stirring rigorously. The progress of the reaction was
monitored with 1H NMR spectroscopy with portions taken for
analysis. The reaction was stopped when complete or after 50 min
(whichever came first), and the resulting product was extracted in
EtOAc (50 mL) and vacuum filtered to recover the catalyst. The
filtrate was transferred to a separating funnel and washed with distilled
water (25 mL) followed by saturated brine (20 mL). The organic
phase was collected and dried over anhydrous MgSO4, run through a
narrow column packed with Amberlyst 15 ion exchange resin, and the
resulting solution concentrated on the rotary evaporator. Product
identification was done by IR spectroscopy, ESI mass spectrometry,
CHN elemental analysis, and 1H and proton-decoupled 13C NMR
spectroscopy. The total product mass recovered, spectroscopic
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assignment (NMR, IR, and ESI-MS), and elemental analysis for the
ring-opened epoxides are provided in the SI.
Dynamic Surface Tension (DST) Measurement of Synthe-
sized Surfactants. To a sodium chloride solution (100 mL, 10
mmol) was added 0.1 g of surfactant to give a 1 g/L surfactant
solution and left to age for 24 h. Thereafter, 5 mL of the solution was
measured in a beaker and placed under a maximum-bubble-pressure
tensiometer, and a precision capillary was immersed automatically to a
depth of 10 mm from the liquid surface. The other end of the capillary
was connected to a gas supply with a pressure sensor, and the
tensiometer was operated to obtain a set of data. The surface lifetimes
of the bubbles were measured until 100 s.
Equilibrium Surface Tension (EST) Measurement of the
Synthesized Surfactants. To a sodium chloride solution (100 mL,
10 mmol) was added 0.1 g of surfactant in a 100 mL sample bottle to
give a 1 g/L surfactant solution, which was left to age for 24 h.
Thereafter, 30 mL of the solution was measured in a clean beaker and
placed under a Kruss K100 tensiometer fitted with a platinum plate
(Wilhelmy plate). The dilute aqueous surfactant solution was then
allowed to attain 25 °C, after which the plate was automatically
lowered into the solution by the automatic interface detection method
to start the experiments. A bottle on a Dosino unit coupled to the
tensiometer was filled with 10 mmol/L sodium chloride solution,
from which the sample was multiply diluted and the instrument run
under preset conditions. An extended surfactant program was used
and sets of measurements were taken until the change in surface
tension was less than 0.1 mN/m. The plate was washed each time
sequentially with ethanol and acetone, dried on a spirit lamp, and then
allowed to cool prior to and after each time the measurement was
made.
■ RESULTS AND DISCUSSION
Synthesis of Alkyl Oleates via Transesterification of
MO. A set of oleate esters were synthesized from methyl oleate
via transesterification with ethanol, 1-propanol, 2-propanol, 1-
butanol, 2-butanol, 1-octanol, 2-octanol, and 1-decanol using
potassium fluoride on alumina support (KF/Al2O3), magne-
sium oxide treated at 600 °C (MgO-T600), and titanium(IV)
isopropoxide (Ti(O-iPr)4) as catalysts (Scheme 1). Trans-
Scheme 1. Transformation of Methyl Oleate into Alkyl
Oleate Esters Using Both Homogeneous and
Heterogeneous Catalysts
esterification of methyl oleate with the various alcohols was
observed to be fastest in reactions involving Ti(O-iPr)4,
presumably as the catalyst was homogeneous with the
reactants.
Transesterification generally gave high conversions, yields,
and selectivities, becoming close to quantitative in most
reactions (Table 1, entries 1−10). However, in the syntheses
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of 1-octyl oleate, 2-octyl oleate, and 1-decyl oleate, the
selectivity was reduced to between 95 and 98% (entries 11−
15). The conversion remained quantitative, with formation of
some side products (Scheme 2 and SI section 6).20 GC-FID
and GC-MS data showed the presence of the corresponding
epoxides and diols in both the crude and final products.
The colors of the synthesized oleates and catalytic studies
(other heterogeneous supports, optimum catalyst loading,
catalyst reuse, and catalyst recovery) were also investigated in
this study and are presented in section 6 of the Supporting
information SI. Alkyl oleates were characterized with FT-IR
spectroscopy, GC-MS, ESI-MS, and one-dimensional (1D)
and two-dimensional (2D) NMR spectroscopy. Full details of
NMR assignment and analytical data are included in the SI.
Epoxidation of Alkyl Oleates. All of the oleate esters
synthesized and methyl oleate for comparison were epoxidized
effectively using H2O2 as the oxidant in the presence of a
catalyst. Two catalytic methods were used to synthesize the
epoxides. The first method involved the use of a preformed
commercial phosphotungstic acid (PTA), while the second
method involved the preparation of PTA in situ by the reacting
tungsten powder, hydrogen peroxide, and orthophosphoric
acid (H3PO4), and both methods used Adogen 464 as the
phase transfer catalyst (PTC), as shown in Scheme 3.
Typically, a catalyst concentration of 6 wt % relative to alkyl
oleate and 3 wt % Adogen 464 concentration relative to oleate
were applied in all epoxidation reactions.
Conversion, yield, and selectivity were calculated and are
presented in Table 2. Alkyl oleate conversion up to 99%, yield
up to 93%, and selectivity up to 95% for synthesis involving the
preformed PTA catalyst were obtained. Side reactions are
commonly observed with fatty acid alkyl ester (FAAE)
epoxidation.7,21,22 As such, the following side products were
detected alongside the desired epoxides: nonanal, 9-oxo-alkyl
ester nonanoic acid, cis-9,10-epoxy octadecanoic acid, and diol.
The reaction times were determined by monitoring the
conversion and yield and differed from one epoxide to the
other. It was noted that those oleates in which waxes were
formed (Table 2 entries 1, 2, 3, and 5; SI section 6.0 and
Figure SI-4a) took longer reaction times to reach a comparable
level of conversion compared with those in which there were
no waxes (entries 4 and 6). This could be due to reduced
molecular collision of reactants resulting from the increased
viscosity and reduced mobility of the oleate molecules.
Comparing the two epoxidation methods, preformed PTA
catalysis gave the least side products and as such was preferred.
Precise carbon and proton NMR spectra assignment was
achieved by a combination of COSY, HSQC, and DEPT
carbon as detailed in the SI Section 4.0. IR spectral analysis
(Figure SI-8) equally showed the disappearance of the ca. 3004
cm−1 band belonging to the olefinic C−H stretch and
appearance of vibrations belonging to the epoxy band between
953 and 979 cm−1 (asymmetric deformation) and between 822
and 837 cm−1 (symmetric ring deformation). The epoxy bands
are in line with the values reported in the literature.23,24
Electrospray ionization mass spectrometry was employed to
determine the accurate masses for all of the epoxides
synthesized.
With respect to the appearance of the alkyl oleate epoxides
synthesized, it was observed that there was a change in color
from deep to light amber shades in the compounds formed as
shown in Figure SI-9. This was probably due to the bleaching
of the oleates by hydrogen peroxide.
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Table 1. Comparative Effectiveness of Ti(O-i-Pr)4, MgO-T600, and KF/Al2O3 Catalysts for Alkyl Oleate Synthesis
entry alcohol oleate ester product catalyst time (h) conversiona (%) selectivity (%) yielda (%)
1 ethanol ethyl oleate KF/Al2O3 30 99 100 99
2 ethanol ethyl oleate Ti (O-i-Pr)4 10 99 100 99
3 propan-1-ol 1-propyl oleate KF/Al2O3 30 99 100 99
4 propan-1-ol 1-propyl oleate Ti (O-i-Pr)4 10 99 100 99
5 2-propanol 2-propyl oleate KF/Al2O3 36 98 100 98
6 2-propanol 2-propyl oleate Ti (O-i-Pr)4 24 100 100 100
7 butan-1-ol 1-butyl oleate KF/Al2O3 24 100 100 100
8 butan-1-ol 1-butyl oleate Ti (O-i-Pr)4 10 96 100 96
9 butan-2-ol 2-butyl oleate KF/Al2O3 30 100 100 100
10 butan-2-ol 2-butyl oleate Ti (O-i-Pr)4 10 98 100 98
11 octan-1-ol 1-octyl oleate MgO-T600 24 100 95 95
12 octan-1-ol 1-octyl oleate Ti (O-i-Pr)4 13 100 88 88
13 octan-2-ol 2-octyl oleate MgO-T600 39 100 98 98
14 octan-2-ol 2-octyl oleate Ti (O-i-Pr)4 17 100 97 97
15 decan-1-ol 1-decyl oleate MgO-T600 24 100 98 98
a
Calculated by GC. Reaction conditions: methyl oleate (20 g, 67.2 mmol), alcohol (403 mmol), and catalyst (2 g, 10 wt % with respect to methyl
oleate) under reflux temperatures of the respective alcohol.

Scheme 2. Formation of Aldehydes, Keto Esters, Epoxides, and Diols Observed in Higher Alkyl Oleates during
Transesterification of Methyl Oleate Leading to Reduced Selectivity

Scheme 3. Synthesis of Alkyl Oleate Epoxide from the
Oxidation of Alkyl Oleate in the Presence of Hydrogen
Peroxide via Either Preformed PTA or In Situ PTA
Catalysis
Ring Opening of Alkyl Oleate Epoxides with PEGs.
Many of the previous studies involving ring opening of methyl
1860
oleate and fatty acid epoxides utilized the boron trifluoride
catalyst.14,18,25,26 However, boron trifluoride’s acceptance as an
effective catalyst for this reaction continues to wane not only
because it is a homogeneous catalyst but also because of its
high toxicity. Some heterogeneous catalysts such as saponite
clays and Nafion-silica have been reported as being effective for
epoxide ring opening of epoxy methyl oleate.27,28 However,
their effectiveness with longer-chain fatty esters is unknown.
This study sought to catalyze the ring-opening step using
heterogeneous catalysts that are eco-friendly and cheap.
The synthesized epoxides were ring-opened with mono-
methylated PEGs (MePEG) and uncapped PEG diols (PEG)
using Lewis acid catalysts (Scheme 4). A wide range of
homogeneous and heterogeneous metal and non-metal Lewis
acid catalysts were first screened at different reaction
conditions: ytterbium(III) triflate, Yb(TFA)3; indium(III)
triflate, In(TFA)3; iron(III) triflate, Fe(TFA)3; scandium(III)
triflate, Sc(TFA)3; silica-supported boron trifluoride, Si-BF3;
boron trifluoride diethyl etherate, BF3-Et2O; sulfuric acid,
H2SO4; iron(III) chloride, FeCl3; iron-exchanged montmor-
illonite clay, Fe-mont; aluminum-exchanged montmorillonite
clay, Al-mont; and aluminum-exchanged zeolite clay, Al-
zeolite. Most of these catalysts are less well known for this
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Table 2. Table Effectiveness of Preformed PTA for Synthesis of Alkyl Oleate Epoxides
entry oleate epoxide time (h) conversiona (%) selectivity (%) yielda (%)
1 methyl oleate epoxide 3.5 99 73 73
2 ethyl oleate epoxide 5.5 98 95 93
3 1-propyl oleate epoxide 5.5 95 92 88
4 2-propyl oleate epoxide 3.0 100 93 93
5 1-butyl oleate epoxide 6.0 95 83 79
6 2-butyl oleate epoxide 3.0 99 82 81
7 1-octyl oleate epoxide 3.0 99 84 83
8 2-octyl oleate epoxide 3.5 95 81 77
9 1-decyl oleate epoxide 3.0 99 90 90
a
Calculated by GC. Reaction conditions: alkyl oleate (100.15 mmol), H2O2 (40 mL), water (30 mL), PTA (6 wt % with respect to alkyl oleate)
and Adogen 464 (3 wt % with respect to alkyl oleate) at 50°C, t = 3 h.

Scheme 4. Synthesis of PEGylated Oleate Esters from the
Ring Opening of Alkyl Oleate Epoxides with PEGs of
Varying Chain Length Catalyzed by Heterogeneous Lewis
Acids
type of reaction.29,30 The metal-exchanged montmorillonite
catalysts were prepared as earlier reported.17,31,32
Results of catalyst screening (SI section 9.0 Table SI-4)
showed that Si-BF3 gave high selectivity toward the PEGylated
oleate esters. Heterogeneous silica-supported BF3 is corrosive
but significantly less hazardous than its unsupported free
form.33,34 In order to accurately characterize the resulting
PEGylated oleate esters owing to their high molecular masses,
model reactions with lower-molecular-weight compounds
(<726 g/mol) of the same functionalities as PEGs were
investigated and the products were characterized with GC-
FID, GC-MS, IR spectroscopy, and proton-decoupled NMR
spectroscopy. The reactions involved ring-opening cyclohexene
oxide (CHexO) and methyl oleate epoxide (EMO) with
ethylene glycol (EG), triethylene glycol (TEG), poly(ethylene
glycol) (PEG), and 2-methoxyethanol (MeEG).20 From the
model reaction, based on the yield and selectivity, the best
catalysts selected for synthesis were determined to be Si-BF3
and Fe-mont. Subsequently, epoxides of methyl, ethyl, 1-
propyl, 2-propyl, 1-butyl, 1-butyl, 1-octyl, 2-octyl, and 1-decyl
oleates were ring-opened with poly(ethylene glycol) 400 (PEG
400), poly(ethylene glycol) 1000 (PEG 1000), poly(ethylene
glycol) 1500 (PEG 1500), methoxy poly(ethylene glycol) 400
(MePEG 400), and methoxy poly(ethylene glycol) 750
(MePEG 750). PEGs with molecular weight less than 1000
are viscous and colorless liquids, while higher-molecular-weight
PEGs are waxy white solids.
Synthesis of the PEGylated oleate esters was typically
performed by heating PEGs or MePEGs to 80 °C and adding
the catalyst, followed by dropwise addition of the fatty epoxide
over 5 to 10 min depending on the amount of epoxide added.
The initial ring-opening reactions were catalyzed by the Si-BF3
catalyst with a typical reaction time of 50 min. A catalyst
loading of 1 and 2 wt % amount of Si-BF3 relative to PEG or
MePEG was first applied, but there was no conversion after 2 h
of reaction; thus, 5 wt % Si-BF3 was used for further synthesis.
Different catalyst concentrations were initially applied for the
metal-exchanged mont catalysts, but 20 wt % catalyst
concentration gave the best conversion in 2 h. Interestingly,
20 wt % each of Al-mont, Fe-mont (NO3−) was prepared from
the nitrate salt of iron, and Fe-mont (Cl3−) was prepared from
the chloride salt of iron; catalysts relative to PEG were found
as effective as the 5 wt % Si-BF3 catalyst in 2 h of the reaction.
However, Fe-K30-mont was not effective at these conditions as
a large portion of the epoxide was instead converted to diol.
The metal-exchanged mont catalyst generates products with a
pale amber color (Figure SI-12), which will easily blend with

Table 3. Description of PEGylated Oleate Esters Synthesized from PEGs of Different Chain Lengths

mass av. molecular weight

PEG color appearance and texture recovery (%) range (g/mol)
PEG 400 golden amber viscous ∼77 726−852
MePEG a different shade of less viscous 97 739−865
400 amber
MePEG golden amber gel-like viscous 90 1049−1175
750
PEG 1000 amber viscous when hot but solidify into hard-to-cut-through materials at room 95 1298−1424
temperature
PEG 1500 golden amber golden amber hard-to-cut-through materials at room temperature 93 1826−1952

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most cosmetic formulations. Completion of the reaction was mont catalyst used for the ring-opening reaction. This indicates
usually marked with a change in the reaction mixture color that there has been some degree of catalyst leaching in each
from amber to golden amber or brown. Excess PEG was step of the synthesis, although the presence of these metals
removed by transferring the filtrate (the resulting solution may not impair surfactant end-application performances as
following catalyst removal) into a separating funnel; after their overall concentrations are low (W is the highest at 600
adding water, the solution was shaken to form an emulsion, ppm). The Al content is below that typically found in many
which was broken up with the addition of brine. However, foodstuffs;35 potassium and iron are not problematic, while
attempts to remove excess MePEG by the same method were dermal exposure to W is not problematic at the concentrations
unsuccessful. Therefore, syntheses involving MePEG and other recorded.36
higher PEG chains were subsequently carried out using an Physicochemical Performance of the Synthesized
equimolar amount of epoxide and PEG. Compounds. DST of the Synthesized PEGylated Oleate
A descriptive summary of the synthesized PEGylated oleate Esters. Dynamics studies of the synthesized PEGylated oleate
esters from different PEGs is presented in Table 3. The average esters including surface tension and critical micelle concen-
molecular weight ranges from 726 to 1952 g/mol with a tration (CMC) measurements were recorded using a Sinter-
minimum product recovery of over 77%. The amber-shaded face maximum-bubble pressure tensiometer and a Kruss K100
products varied from viscous to hard-to-cut-through waxy tensiometer coupled with Metrohm 700 dosino. The extended
materials. surfactant characteristic method was used to measure the
Characterization of Synthesized PEGylated Oleate CMC. DST gave information on surface tension as a function
Esters. Model reactions of methyl oleate epoxide with TEG of time. The results for some of the compounds are shown in
and PEG 400 using the Si-BF3 catalyst already gave a minimum Figure 1. The synthesized molecules demonstrated surface
product yield of 75%. The final PEGylated oleate esters were
characterized with 1D and 2D NMR spectroscopy, FT-IR
spectroscopy, electrospray ionization mass spectrometry, CHN
elemental analysis, and inductively coupled plasma mass
spectrometry (ICP-MS).
NMR, IR, and ESI Analyses. Full details of the
characterization and peak assignments of all synthesized
surfactants are provided in sections 5.0 and 9.0 of the SI.
Specific details of NMR, IR, and ESI using PEGylated methyl
ester as an example are provided in sections 9.1−9.4 of SI.
CHN Elemental Analysis. It became apparent that some
of the synthesized PEGylated oleate esters contained residual
Adogen 464; thus, the PEGylated oleate ester-ethyl acetate
mixture was passed through a narrow column packed with
Amberlyst 15 ion exchange resin to remove the cationic
surface-active impurity and the resulting compounds were
investigated using a CHN elemental analyzer. The results are
presented in Table 4 and it was attested that nitrogen was not

Table 4. CHN Elemental Composition of Epoxide and

PEGylated Oleate Esters after Treatment with an Ion
Exchange Resin
Figure 1. Dynamic surface tension of unpurified PEMO 400,
percentage found after ring opening and MPEMO 400, PEEO 400, PEEO 1500, PE2BO 400, PE2BO 1500,
treatment PEOO 400, PEOO 1500, PE2OO 400, and PE2OO 1500.
entry compound code C H N
1 PEMO 400 60.673 10.089 ND
activity with good dynamics. PEMO 400 (hydroxyl end group
2 MPEMO 750 57.262 9.637 ND
to PEG chain) had the lowest surface tension (32 mN/m),
3 PE2BO 400 63.418 10.395 ND
while PEOO 400 had the highest surface tension (53 mN/m).
4 PEMO 1500 55.236 8.782 ND
MPEMO 400 (methoxy end group to PEG chain) with a
surface tension of 33 mN/m did not perform any differently
detected (ND) in any of the surfactants after purification with from the hydroxyl end group to the PEG chain and appeared
Amberlyst 15 resin, which implies that Adogen 464 impurity to have reached equilibrium in 20 s. It was observed that
had been successfully removed by this approach. PEEO 400 had a lower surface tension (32 mN/m) but
ICP Mass Spectrometry. Determination of residual metal quicker equilibrium time compared to PEEO 1500 with higher
catalysts in PEGylated oleate esters was achieved using ICP- surface tension (42 mN/m) and it took a bit longer to
MS. Results for PEEO 400 obtained via Fe-mont catalysis equilibrate due to the dominance of the hydrophilic chain over
showed 0.002 wt % (20 ppm) aluminum (Al), 0.009 wt % (90 the hydrophobic chain. PEOO 400 had a high surface tension
ppm) potassium (K), 0.011 wt % (110 ppm) iron (Fe), and (53 mN/m) but slow equilibration, which could be due to the
0.06 wt % (600 ppm) tungsten (W). Al and K were likely presence of an inadequate hydrophilic character over a long
resulting from use of the KF/Al2O3 transesterification catalyst, hydrophobe. PEOO 1500 also was slow but not at equilibrium
while W most likely comes from phosphotungstic acid used to due to the high molecular weight, which delays self-
catalyze the epoxidation process. Fe has come from the Fe- aggregation. However, the latter has a lower surface tension
1862 https://doi.org/10.1021/acssuschemeng.2c06298
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ACS Sustainable Chemistry & Engineering
Figure 2. Surface tension versus the logarithm of surfactant concentration for purified PEMO 400 (1 mg/mL) and PEEO 400 (1 mg/mL) at ∼26
°C.
(49 mN/m) than the former, thus having a better balance
between hydrophobic and hydrophilic regions.
Structurally contrasting between the PEGylated molecules, it
was observed that as the PEG chain length increased from 400
to 1500, although surface tension increased due to increasing
hydrophilicity in the PEG chain except in PEOO where it
decreased, equilibrium times were longer. Increasing the alkyl
group on the ester functionality across the same PEG chain
length did not significantly increase the surface tension and
equilibrium time upon the addition of four CH2 groups.
However, a significant increase was recorded with the addition
of eight CH2 groups to the ester.
EST of the Synthesized PEGylated Oleate Esters.
Measurements of equilibrium surface tension using a Kruss
K100 tensiometer showed the variation between the surface
tension and change in surfactant concentration. A surfactant
loading of 1 mg/mL was prepared and diluted by the
instrument while changes in surface tension were measured.
Continual dilution to a concentration low enough to give the
surface tension of water (72 mN/m) was not achieved for all
measurements. Initial attempts with unpurified surfactants are
reported in the ESI section 11. Results for the purified samples
are shown in Figure 2 and compared with the unpurified
samples (Figure SI-13). The surface tension vs concentration
curves showed that PEEO 400 at 0.001 mg/L concentration
when purified was 58 mN/m, while when unpurified it was 45
mN/m.
The higher surface tension in the purified sample is as a
result of the removal of surface-active impurities. The same
trend was observed in the purified and unpurified PEMO 400
surfactant curves in which surface tension increased from
around 40 mN/m to over 46 mN/m at 0.3 mg/mL
concentration after removing the impurities. CMC values for
both purified PEMO 400 and PEEO 400 were ∼0.7 and ∼0.1
mg/mL, respectively, close to what was recorded for the
unpurified samples. With both having the same hydrophilic
head group, CMC is eight times lower for PEEO 400 with an
addition of one CH2 to the hydrophobic tail. This observed
factor of 7 reduction is far more than a factor of about 3 that
1863
pubs.acs.org/journal/ascecg Research Article
Traube’s rule states upon adding a methylene group to
nonionics.37−39 The structural difference in surfactant types
could be the likely reason for this observation. However, it is
not obvious how this is linked with surface tension and CMC
reduction. With a lower CMC, PEEO 400 is a better surfactant
than PEMO 400 depending on their area of application. Both
PEEO 400 and PEMO 400 surfactants have an effectiveness of
∼40.5 mN/m when extended to the surface tension of water
(Figure 2). Efficiency could not be evaluated for PEMO 400
(unless the concentration was extended), but PEEO 400
recorded an efficiency of 0.018 mg/mL. Efficiency is the
concentration required to reduce the solution surface tension
by 20 mN/m. This value is similar to that obtainable in
commercial nonionic surfactants.40 CMC is sensitive to both
the presence of alkyl chain length and EO number in polymeric
surfactants. However, it is more sensitive to an increase in the
former than in the latter.38 Therefore, for other surfactants
where measurements were not taken, CMC values will be
higher for all surfactants on increasing the alkyl chain length
attached to the ester at a constant EO number, but lower
CMCs will be expected for those having the same alkyl chain
length as the EO number increases from 9 to 16 and from 22
to 34.
Hydrophilic−Lipophilic Balance (HLB). The HLB
concept using the extended contribution effective chain length
(ECL) method was employed as a rapid and facile approach to
predict the possible properties and applications of the
PEGylated oleate esters as surfactants (Figures 3−6, further
details of the calculations are in the SI, section S11). HLB
values decrease with increasing alkyl group in the fatty chain,
but increase with increasing EO number in the hydrophilic
head. Based on the HLB values and range in Figures 3 and 4,
surfactants with PEG 400, MePEG 400, and MePEG 750 (EO
number 9 and 16) will likely find applications as either oil-in-
water emulsifiers or detergents. Surfactants with higher EO
number (PEG 1000) spread between three potential
applications. For PEMO 1000 to PE2BO 1000 with HLB
values between 16.70 and 15.33, their potential application will
be as solubilizing agents, while PEOO 1000, PE2OO 1000, and
https://doi.org/10.1021/acssuschemeng.2c06298
ACS Sustainable Chem. Eng. 2023, 11, 1857−1866
ACS Sustainable Chemistry & Engineering
Figure 3. HLB values and average molecular weight obtained for alkyl
oleate surfactants based on PEG 400 and MePEG 400.
Figure 4. HLB values and average molecular weight obtained for alkyl
oleate surfactants based on MePEG 750.
PEDO 1000 surfactants have potentials as either oil-in-water
emulsifiers or detergents (Figure 5). Surfactants with PEG
1500 attached also have three potential applications. The
methyl-, ethyl-, 1-propyl-, 2-propyl-, 1-butyl-, and 2-butyl-
oleate PEGylated surfactants will most likely find applications
as solubilizing agents while the 1-octyl-, 2-octyl-, and 1-decyl-
oleate PEGylated surfactants have potentials as oil-in-water
emulsifiers and detergents (Figure 6). Although HLB values
obtained for isomeric surfactants of the same EO chain length,
for example, 1-propyl oleate- and 2-propyl oleate-based
surfactants, showed no obvious difference, it is believed critical
parking parameter (CPP) values will be different for these
surfactants.
■ CONCLUSIONS
Forty-five renewable nonionic surfactants have been success-
fully prepared from alkyl oleate epoxides via ring-opening
reaction with PEGs of varying chain lengths using cheap
heterogeneous catalysts, affording ∼80% surfactant yield. The
surfactants so formed took the physical form of the PEG
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pubs.acs.org/journal/ascecg Research Article
Figure 5. HLB values and average molecular weight obtained for alkyl
oleate surfactants based on PEG 1000.
Figure 6. HLB values and average molecular weight obtained for alkyl
oleate surfactants based on PEG 1500.
attached to them and were extensively characterized. Treat-
ment of surfactants with Amberlyst 15 resin helped in removal
of the residual Adogen 464 impurity in the epoxidation step,
but it contained trace amounts of residual catalyst metals used
in transesterification, epoxidation, and ring opening processes.
DST studies revealed that structural modifications in the
PEG chain length and alkyl group on the ester functionality
had influence on the surface tension and equilibrium time of
the traditional methyl molecule. The lower-molecular-weight
surfactants were more spontaneous in reaching equilibrium
than the higher-molecular-weight surfactants. EST measure-
ments showed that the surfactants tested have low CMCs
(0.1−0.7 mg/mL) and are efficient and effective. These results
clearly demonstrate that the synthesized surfactants have
suitable properties for use in formulations and that structure
variation has altered these properties accordingly. Based on the
theoretical HLB results, the family of synthesized surfactants
will potentially find applications as oil-in-water emulsifiers,
detergents, solubilizers, and wetting agents, their final use
being heavily dependent on the structure (size of alkyl group
on the ester and length of the PEG chain).
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ACS Sustainable Chem. Eng. 2023, 11, 1857−1866
ACS Sustainable Chemistry & Engineering
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acssuschemeng.2c06298.
synthesis of methyl oleate; spectroscopic assignment
(NMR, IR and ESI-MS) analysis for synthesized methyl
oleate and alkyl oleates; synthesis of alkyl oleates via
transesterification of methyl oleate; preparation of
catalysts; spectroscopic assignment (NMR, IR and
ESI-MS) analysis for alkyl oleate epoxides; spectroscopic
assignment (NMR, IR and ESI-MS) and elemental
analysis for ring-opened alkyl oleate epoxides; details of
transesterification reactions and catalyst loading and
reuse; epoxidation of alkyl oleate; screening of ring-
opening catalyst and characterization of pegylated oleate
esters; synthesized surfactants and their colors; equili-
brium surface tension of synthesized surfactants; HLB
calculations (PDF)
■ AUTHOR INFORMATION
Corresponding Authors
Joseph K. Ogunjobi − Green Chemistry Centre of Excellence,
Department of Chemistry, University of York, York YO10
5DD, United Kingdom; Department of Chemistry, The
Federal University of Technology, PMB 704 Akure, Nigeria;
DWI-Leibniz Institute for Interactive Materials, RWTH
Aachen University, D-52074 Aachen, Germany;
orcid.org/0000-0001-9276-7310; Email: jkogunjobi@
futa.edu.ng
Con Robert McElroy − Green Chemistry Centre of Excellence,
Department of Chemistry, University of York, York YO10
5DD, United Kingdom; School of Chemistry, University of
Lincoln, Joseph Banks Laboratories, Lincoln LN6 7DL,
United Kingdom; orcid.org/0000-0003-2315-8153;
Email: rob.mcelroy@york.ac.uk
Authors
Thomas J. Farmer − Green Chemistry Centre of Excellence,
Department of Chemistry, University of York, York YO10
5DD, United Kingdom; orcid.org/0000-0002-1039-7684
James H. Clark − Green Chemistry Centre of Excellence,
Department of Chemistry, University of York, York YO10
5DD, United Kingdom; orcid.org/0000-0002-5860-2480
Complete contact information is available at:
https://pubs.acs.org/10.1021/acssuschemeng.2c06298
Author Contributions
Conceptualization, C.R.M., T.J.F., J.K.O., and J.H.C.; method-
ology, J.K.O., T.J.F., and C.R.M.; formal analysis, J.K.O.;
investigation, J.K.O.; data curation, J.K.O.; writing�original
draft preparation, J.K.O.; writing�review and editing, all
authors; visualization, J.K.O.; funding, all authors; supervision,
T.J.F., C.R.M., and J.H.C.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
The authors would like to thank Unilever PLC, UK; TETfund,
Nigeria; and the Wild fund, UK for providing funds to support
this study.
1865
pubs.acs.org/journal/ascecg Research Article
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